F:Flammable;
111-34-2Relevant articles and documents
N,N-Dimethylformamide-stabilised palladium nanoparticles combined with bathophenanthroline as catalyst for transfer vinylation of alcohols from vinyl ether
Tabaru, Kazuki,Nakatsuji, Masato,Itoh, Satoshi,Suzuki, Takeyuki,Obora, Yasushi
supporting information, p. 3384 - 3388 (2021/05/03)
We reportN,N-dimethylformamide-stabilised Pd nanoparticle (Pd NP)-catalysed transfer vinylation of alcohols from vinyl ether. Pd NPs combined with bathophenanthroline exhibited high catalytic activity. This reaction proceeded with low catalyst loading and the catalyst remained effective even after many rounds of recycling. The observation of the catalyst using transmission electron microscopy and dynamic light scattering implied no deleterious aggregation of Pd NPs.
Calcium Carbide Looping System for Acetaldehyde Manufacturing from Virtually any Carbon Source
Rodygin, Konstantin S.,Lotsman, Kristina A.,Ananikov, Valentine P.
, p. 3679 - 3685 (2020/06/17)
A vinylation/devinylation looping system for acetaldehyde manufacturing was evaluated. Vinylation of iso-butanol with calcium carbide under solvent-free conditions was combined with hydrolysis of the resulting iso-butyl vinyl ether under slightly acidic conditions. Acetaldehyde produced by hydrolysis was collected from the reaction mixture by simple distillation, and the remaining alcohol was redirected to the vinylation step. All the inorganic co-reagents can be looped as well, and the full sequence is totally sustainable. A complete acetaldehyde manufacturing cycle was proposed on the basis of the developed procedure. The cycle was fed with calcium carbide and produced the aldehyde as a single product in a total preparative yield of 97 %. No solvents, hydrocarbons, or metal catalysts were needed to maintain the cycle. As calcium carbide in principle can be synthesized from virtually any source of carbon, the developed technology represents an excellent example of biomass and waste conversion into a valuable industrial product.
Method of producing vinyl ether
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Paragraph 0074, (2016/10/08)
PROBLEM TO BE SOLVED: To provide a method for producing vinylether which gives high conversion rate of ether exchange reaction, excels in recyclability of raw material components and enables mass production at low cost industrially. SOLUTION: This method comprises: performing an ether exchange reaction between vinylethers and alcohols in the presence of a transition metal catalyst; and during the reaction or after completion of the reaction, while bubbling oxygen in the reaction mixture, distilling low boiling point components out to concentrate the reaction mixture. The low boiling point components may be distilled at around 50-100°C. In this reaction, the vinylethers may be used at a rate of excess molar equivalent to the alcohols. The oxygen may be bubbled at a rate of 5-100 L/min to 1 mole of the transition metal catalyst. The transition metal catalyst may be a paradium complex and/or cobalt complex. COPYRIGHT: (C)2013,JPOandINPIT
Nucleophilic addition to acetylenes in superbasic catalytic systems: XIII. Fluoride cesium containing systems, efficient catalysts for alkanols vinylation
Oparina,Shaikhudinova,Parshina,Vysotskaya,Preiss,Henkelmann,Trofimov
, p. 656 - 660 (2007/10/03)
New catalytic systems CsF-MOH (M = Li, Na) were developed for the synthesis of alkyl vinyl ethers comparable in efficiency to cesium alcoholates. The addition of primary and secondary alcohols to acetylene occurs in the presence of these systems at the atmospheric (DMSO, 100°C) or at enhanced (without solvent, 135-140°C) acetylene pressure and affords alkyl vinyl ethers in up to 93% yield. 2005 Pleiades Publishing, Inc.
A structure-reactivity correlation with three slopes in the elimination kinetics of 2-substituted ethyl N,N-dimethyl-carbamates in the gas phase
Chuchani, Gabriel,Nunnez, Oswaldo,Marcano, Norka,Napolitano, Suvighey,Rodriguez, Henry,Dominguez, Marianella,Ascanio, Judany,Rotinov, Alexandra,Dominguez, Rosa M.,Herize, Armando
, p. 146 - 158 (2007/10/03)
The elimination kinetics of 17 2-substituted ethyl N,N-dimethylcarbamates in the gas phase were determined in the temperature range of 269.5-420.2°C and the pressure range of 24-186 Torr. The reactions in a static system and in the presence of a free radical inhibitor are homogeneous and unimolecular and follow a first-order rate law. The kinetics and thermodynamic parameters are described. The use of several structure-reactivity relationship methods meaningless results, except for Taft σ* values. Three good slopes are originated at σ*(CH3) = 0.00. Slope a: the 2-substituted alkyl groups gave a good straight line when log (k/kCH3) vs σ* values (ρ* = - 1.94 ± 0.30, r = 0.977 at 360°C) were plotted. Slope b: Polar2 substituents gave an approximate straight line with ρ* = - 0.12 ± 0.02, r = 0.936 at 360°C. Slope c:the correlation of multiple bonded and electron-withdrawing substituents interposed by a methylene group at the 2-position of ethyl N,N-dimethylcarbamate was found to give a very good straight line wirh ρ* = 0.49 ± 0.02, r = 0.991 at 360°C. Mechanisms are suggested on the basis of these relationships. The point position of the substituents phenyl (C6H5) and isopropenyl [CH2=C(CH3)] at the 2-position was found to fall far above the three slopes of the lines. These results are interpreted in terms of neighboring group participation of these substituents in the elimination process of the carbamates. However, the acidity of the benzylic and allylic Cβ-H bond for a six-membered cyclic transition state may not be ignored. Copyright
1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one and oxazolo[4,5-b]pyridin-2-(3H)-one compounds
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, (2008/06/13)
The invention relates to a compound selected from those of formula (I): STR1 wherein R1, W and Y are as defined in the description, its geometric and/or optical useful as anti-algies.
Process for preparing unsaturated ethers
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, (2008/06/13)
A process for preparing unsaturated ethers of the formula (1) STR1 from acetals or ketal of the formula (2) STR2 is improved by heating the acetals or ketals at from 100° to 250° C. in a high-boiling, branched carboxylic acid and obtaining the unsaturated ether as a distillate. The process, which is insensitive to contaminants, gives the unsaturated ether in high yields.
PYROLYTIC TRANSFORMATION OF THE VINYL MONOETHERS OF DIOLS IN THE PRESENCE OF ALKALIS
Trofimov, B. A.,Oparina, L. A.,Parshina, L. N.,Lavrov, V. I.,Grigorenko, V. I.,Zhumabekov, M. K.
, p. 1424 - 1428 (2007/10/02)
The alkaline pyrolysis of the vinyl monoethers of diols takes place at 170-250 deg C and is accompanied by cycloacetalization (ethylene glycol, 1,3-propanediol), by processes involving cleavage of the C-O bonds (diethylene glycol, 1,4-butanediol), and also by the release of hydrogen, carbon dioxide, methane, ethane, acetylene, and C3 to C5 hydrocarbons.Distillation of ethylene glycol vinyl monoether with potassium hydroxide, sodium hydroxide, and lithium hydroxide can result in explosion as a result of the vigorous and exothermic release of gas.
PREPARATION OF BUTYL VINYL ETHER AND BUTANOL BY CATALYTIC PYROLYSIS OF DIBUTYLACETAL (ACETALDEHYDE DIBUTYL ACETAL).
Lavrov,Parshina,Zhumabekov,Grigorenko,Trofimov
, p. 409 - 410 (2007/10/02)
A considerable amount of dibutylacetal is formed as a by-product during industrial production of butyl vinyl ether by vinylation of butanol. In order to obtain additional amounts of butyl vinyl ether and butanol, i. e. , in effect to raise the yield of the end product, the authors studied thermal decomposition of dibutylacetal in presence of various catalysts. Examination of the results shows that dibutylacetal is resistant to pyrolysis in presence of quinoline, potash, and aluminum oxide. The conversion of dibutylacetal is 5-6%. When heated in presence of acid catalysts, dibutylacetal decomposes to form butyl vinyl ether and butanol. For example, with a mixture of quinoline and phosphoric acid as the catalyst the degree of conversion is 93%, the yield of butanol on the dibutylacetal converted is 95-103%, and the yield of butyl vinyl ether is 70-97%.
